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Two novel 1,10‐phenanthroline‐2,9‐diamide ligands were constructed on the basis of 2‐phenylpyrrolidine and obtained as pure diastereomers. These ligands demonstrated advanced properties in liquid‐liquid extraction tests. They revealed high efficiency of americium(III) extraction alongside with the record values of selectivity in the separation of americium from light lanthanides from strongly acidic media. An abrupt increase of extraction efficiency when moving along the lanthanide series from lanthanum to lutetium was observed. The examination of the extraction behavior of pure diastereomeric forms revealed noticeable differences in their selectivity while maintaining the overall extraction trend. The explanation of the discovered patterns was elucidated by a comprehensive study of the ability of the ligands to bind lanthanide nitrates in solutions. All the data collected (UV‐vis and NMR titration, X‐ray analysis of resulting complexes, solvation numbers estimation) were supported by quantum chemical calculation. These data clearly indicated that in the case of light lanthanides the formation of 1 : 1 complexes is most preferable. At the same time, complexes with heavy lanthanides, such as ytterbium and lutetium, exist as ionic pairs which may consist of [L2M]z+ cations counterbalanced by metallate anions, which may result in the formation of the species of unusual composition like L2M2 or even L4M5 clusters. [ABSTRACT FROM AUTHOR]

A systematic study of extraction systems for the separation of f-elements using the tetradentate N,O-donor diamide of 1,10-phenanthroline-2,9-dicarboxylic acid (L) in various molecular and ionic solvents was performed. It was demonstrated that the nature of a diluent has a significant impact on solvent extraction of Am(III) and Ln(III) and the stoichiometry of formed complexes with f-elements. The mechanism of complexation and forms of complexes in different diluents were investigated by radiometric methods, UV-vis titration, and XRD. [ABSTRACT FROM AUTHOR]

[Display omitted] The first bifunctional materials for simultaneous catalysis and temperature measurements were obtained based on europium and ytterbium complexes with (4,7-dichloro-1,10- phenanthroline-2,9-diyl)bis(pyrrolidin-1-ylmethanone). The complexes demonstrated intense visible and NIR luminescence, the ability to homogeneously catalyze the Henry reaction, and high luminescence sensitivity to temperature (S r = 1.7% K−1). [ABSTRACT FROM AUTHOR]